Process of treating fabrics to render them oil- and water-repellent



United States Patent 3,365,329 PROCESS OF TREATENG FABRKIS T0 RENDER THEM @IL- AND WATER-REPELLENT Malcolm Maclifienzie, Jr., Charlotte, and Roger James Martin, Jr., Greensboro, N.C., assignors to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware N0 Drawing. Filed June 30, 1964, Ser. No. 379,394 2 Claims. (Cl. 117-161) This invention is directed to an improvement in the process of treating fabrics to render them oiland waterrepellent and to provide significant repellencies that are durable to laundering and dry cleaning. More particularly, the present invention deals with the process of treating textile fabrics with (1) relatively small amounts of a fluoroalkyl-containing polymeric composition, (2) a composition comprising a wax and a stearic acid-hexamethylolmelamine derivative or a copolymer of (diethylamino) ethyl methacrylate and octadecyl methacrylate, and, optionally, (3) a crease resistant resin. In this novel process, a significant improvement is obtained by adding, to the dilute treatment bath containing these oiland waterrepellents, a dilute solution of a mixture of a selected anionic surface active agent of the sodium long chain alkyl sulfate or sulfated long chain alkenyl acetate types and a non-ionic surface active agent of a selected ethylene oxide condensation product. When the optional crease resistant resin is present in the treatment bath, only the selected anionic agent is added to obtain the improvement. The unexpected improvement provided by the invention mode of operation is a substantial increase in the initial oiland/or water-repellency of the treated fabric and a high retention of these properties during repeated laundering and/or dry cleaning.

Oleophobic properties are commonly imparted to textile fabrics by treating them with selected polymeric polyfluoro materials. These compounds also impart water repellency. Water repellent effects are, however, commonly obtained with compositions comprising wax and a melamine derivative or a cationic polymeric material. These water repellent agents are often combined with the polyfluoro compositions to enhance the oil repellency and to provide a high water repellency in combination with the oil repellency. The increased oil repellency is advantageous, and the use of the lower cost Wax-containing water repellent permits reducing the amount of the high cost polyfiuoro material required for many applications. Crease resistant resins and other thermosetting resins which are employed, for example, to improve the hand of a fabric are frequently present in a textile treatment bath. These resins also enhance the repellent properties of fabric treated with fluorine-containing agents.

However effective the present combinations of agents are in rendering fabrics repellent (1) to oils and greases as vehicles and bonding agents for soils and (2) to water and water-borne liquid soils, there is room for improvement in keeping fabrics clean and unwetted and unaffected by water. Moreover, such oiland water-repellent textile finishes need to be more durable to laundering and dry cleaning. The deposition on a fabric of lower amounts of the relatively expensive fluorine-containing oil repellent than are now commonly used to obtain a given effect would be both an economic advantage and a significant advance in the art.

It is, therefore, an object of this invention to improve the process of treating textile fibers to provide oiland water-repellency. Another object is to enhance the oiland water-repellency imparted to textile fibers by a combination of a polyfluoro polymeric oil-repellent and a selected wax composition for providing water-repellency. A further object is to increase the oiland water-repellency and the durability of these repellencies to laundering and dry cleaning when the repellencies are provided by compositions containing a relatively low amount of polyfluoro polymer.

These and other objects of the invention will become apparent from the following description and claims.

More specifically, the present invention is directed to the process of treating textile fabrics with (a) a fluoroalkyl-containing polymeric composition to impart oiland water-repellency, and (b) a composition comprising a wax and a member of the group consisting of the acetic acid salt of a condensation product of hexamethylolmelamine, stearic acid, and triethanolamine and a copolymer of 2-(diethylamino)ethyl methacrylate and octadecyl methacrylate as a water repellent, the improvement being one which consists of adding to the dilute treatment bath, with agitation, a 5% to 15% aqueous solution of a mixture consisting of 60 to parts by Weight of a member of the group consisting of sodium C to C alkyl sulfates and the sodium salt of a sulfated C to C alkenyl acetate and 40 to 25 parts by weight of a condensation product of 10 to 20 moles of ethylene oxide and one mole of a member of the group consisting of C to C alkenyl alcohol and p-nonylphenol to provide from about 15% to about 30% by weight of said mixture on the basis of the said fluoroalkyl-containing polymeric composition and impregnating the fabric with the resultant treatment bath. A preferred embodiment is one wherein the treatment bath contains component (a) in an amount to give a pickup on the Weight of the fabric from about 0.2% to about 0.5% of the component, and component (b) is present to the extent of 1 part to 5 parts per part of component (a).

The textile fabrics to which the present improved invention process may be applied include wool, cotton, acetate, nylon, polyacrylic fibers, polyester fibers, and their blends.

COMPONENTS OF TREATMENT BATH (a) F luoroalkyl-containing polymeric composition.- Such a composition is well known in the art for use in imparting oil-repellency and water-repellency to fabrics. The fluoroalkyl groups contained within the composition are perfluoroalkyl groups represented by C F wherein n is an integer 4 to 14.

These groups form the terminal elements of various acrylate and methacrylate esters from which the polymeric material is made. These polymeric esters, copolymore of these esters and other polymerizable vinyl compounds, and mixtures of these copolymers and polymers or copolymers from polymerizable vinyl compounds are used as a water dispersion.

Specific, representative fluoroalkyl-containing polymeric compositions are the polymer, copolymer, and mixed polymer composition containing, as the principal fluorinecontaining component,

wherein n is 4 to 14 as described in copending (common assignee) application Ser. No. 288,894, as well as Belgian Patent 634,720; French Patent 1,327,328 and Swiss Patent 5,274/ 62. Another group of fiuoroalkyl-containing polymers and copolymers have, as the principal fluorine-containing component,

C F SO N(R) R CH OOC(R )=CH (b) Wax water-repellent cmp0siti0n.-The defined composition of this component is well known in the art. It comprises 25% by weight of paraffin wax mixed with the acetic acid salt of the condensation product of hexamethylolmelamine, 2 moles stearic acid, and 1 mole triethanolamine, known in the trade as Phobotex f/t/c and described in US. Patent 2,783,231. In applying Phobotex f/t/c, a catalyst consisting of a mixture of 70 parts by weight aluminum glycolate and 30 parts by weight of glycolic acid is employed in an amount equal to 10% by weight of the Phobotex f/t/c to achieve maximum durability of this particular water-repellent textile finish.

The composition also comprises a dispersion of a mixture of a copolymer of (diethylamino)ethyl methacrylate and octadecyl methacrylate and paraifin wax as described in Example 4 of British Patent 915,759 using 30 parts of the basic monomer to form the comonomer and a waX:copolymer ratio of 3:1.

(c) Crease resistant resin.This optional component of the treatment bath is a thermosetting resin frequently employed to impart crease resistance to a fabric. The resins of this type which may be added to the treatment bath include commercially available urea-formaldehyde resins, melamine-formaldehyde and methylol derivaties of cyclic ethylene ureas, triazonc derivatives, and urons. The use of these resins is accompanied by catalysts designed for the fixation of the resins. The catalysts include amine hydrochlorides, metal salts such as magnesium chloride and zinc nitrate.

When a crease resistant resin is present in the treatment bath only the anionic agent is added in an amount equal to about 2% to 10% of the fluoroalkyl composition.

The relative amounts of the fluoroalkyl-containing polymeric composition and the wax Water-repellent composition in the textile finishing bath affect the degree of oiland water-repellency obtained. For the best results the proportion of these components will vary with different fabrics and conditions of application. In general, a minimum of 0.2% by weight of the fiuoropolymer composition on the weight of the fabric is needed, and more than 0.65% by weight is considered uneconomical. The preferred amounts are within the range of 0.25% to 0.45%. The amount of the wax-containing Water-repellent composition should be adjusted to fall within the range of 1 part to parts per part of the fluoropolymer composition. When the ratio of the wax-containing waterrepellent to the fiuoropolymer composition is much higher than 5:1, the oil repellency is decreased. If the ratio of these components is much less than 1:1, there is a deficiency of the water-repellent component and the water repellency of the finished fabric is decreased.

The crease resistant resin, when applied together with the oiland water-repellents, is deposited to the extent of 1% to 5% by weight on the weight of the fabric. Within this range the ratio of the resin to the fluoropolyrner composition is not critical.

ADDED SURFACE ACTIVE AGENTS The anionic surface active agents of particular value in practicing this invention are sodium C to C alkyl sulfates and the sodium salt of a sulfated C to C alkenyl acetate. These dispersing agents are usually employed in combination with non-ionic surfactants, although they are effective when used alone in a pad bath containing a crease resistant resin in combination with the oiland water-repellents. The non-ionic surface active agents that are blended with the anionic agents are the condensation product of to 20 moles of ethylene oxide with 1 mole of technical oleyl alcohol (C to C .alkenyl alcohol) and the product of 9 to 10 moles of ethylene oxide condensed with 1 mole of p-nonylphenol. The mixture of surface active agents consists of 60 to 75 parts by weight of the anionic agent and 40 to parts by weight of the non-ionic agent. The mixture is added to the treatment bath as a water solution of 5% to 15% concentration to provide from about 15% to about 30% by weight of the mixture of agents on the basis of the fluoroalkyl-containing polymeric composition. When added singly to a treatment bath containing a crease resistant resin a dilute solution of the anionic surfactant of 5% to 15% concentration provides from 2% to 10% by weight of the fiuoroalkyl polymer of the anionic additive.

It is unexpected that the addition to the treatment bath of limited amounts of selected anionic agents, used alone or in combination with certain non-ionic surface active agents, makes possible the marked improvement in the oiland water-repellency and in the durability of these repellencies. These favorable results are particularly surprising because many of the materials normally present in the treatment bath are cationic or are salts of metals which would be expected to be incompatible with watersoluble anionic agents. For instance, many of the fluoropolymer composition dispersions are cationic; so are the wax water-repellent dispersions. The catalysts used in various composites of textile treating agents in the invention process contribute polyvalent metal ions which have an insolubilizing action on anionic surfactants. Heretofore, those skilled in the art of finishing textile fabrics have taken pains to avoid any contamination from anionic surface active agents in the treatment bath. Excessive amounts of the anionic surfactants of the invention process do cause coagulation of the dispersed materials in the treatment bath, but the controlled amounts employed in the manner described give improved finishes on the goods treated according to the invention.

GENERAL PROCEDURE The practice of this invention, in its simplest form, involves the padding of a fabric in a bath containing the fluoropolyrner dispersion together with a dispersed waxcontaining water-repellent composition, its catalyst if needed, and the selected surfactant adjuvants. When the wax-containing water-repellent composition is Phobotex f/t/c, two parts of hot water are mixed with stirring with one part of the water-repellent and heated to the boil to melt the solid material. One-tenth part of the aluminum glycolate-glycolic acid catalyst, is added and the stirring continued to complete the emulsification. The concentrated emulsion is diluted with water at about 38 C. to give of the ultimate volume. The fluoropolymer dispersion is then added with agitation followed by the surfactant adjuvants as a 10% water solution. The bath is adjusted to its final volume with water and is ready for use in the normal manner.

When a crease resistant resin is present in the treatment bath, it is customary to use the anionic surfactant adjuvant alone. In this case, the wax-containing waterrepellent composition is emulsified as described above, the emulsion is diluted with water at about 38 C. and the anionic adjuvant is added as a 10% water solution with efiicient agitation. The crease resistant resin and its catalyst are added followed by the fiuoropolymer dispersion to obtain a bath ready for use.

The treatment bath is used at a temperature within the range of 20 C. to 35 C. in a 2- or 3-roll padder of the type normally employed in applying resins to fabrics. A weight pickup of 40% to is attained, and the concentration of the components of the bath are adjusted accordingly to give the desired dry weight pickup on the weight of the fabric. After padding, the fabric is dried under conditions that are not critical. Frame drying is preferred to can or roller drying to avoid possible transfer of the finishing agents to the can or roller. A curing or heating step follows. The conditions of cure depend upon the heat stability of the textile fiber and the requirements for developing the best repelleney and fastness (to laundering and dry cleaning) properties. Curing times and temperature will also vary with fabric weight and with different pieces of equipment. Usually TESTING OF FABRICS The treated fabric samples are tested for water repelting paper, and the fabric is air-dried, then dried for 15 seconds on each side on a flat press at about 150 C., and ironed. The dry-cleaned specimen is conditioned at least four hours at 20 C. and 65% relative humidity before testing for repellency.

In order to assure good stain and soil resistant performance of fabric in service, it is customary to require a degree of repellency that has been found from experience to be satisfactory in terms of the results of oil- 10 repellency and water repellency tests. Fabrics destined lency by the Standard Test Method 22-1961 of the for use in rainwear and outerwear are required to have Amer can Associatlon of Textile Chemists and Colorists. a minimum spray test rating of 90 initially and 80 after A of denotes no Water Pnetrat1n or surfiflce three standards launderings or three standard dry cleanadhgslon mung of 90 denotes Shght random Wettmg ings as described above. The oil repellency requirement is and so 15 a minimum rating of 6 initially and 5 after three standard The oil repellency test comprises placmg a drop of test launderings or dry c1eam-ngs Fabrics designed for gem o1l carefully on the textile on a flat hor zontal surface. eral apparel draperies, and Slipcovers require a mini After ten seconds any penetratlon or WICklIlg into the mum spray test rating initially of 80 and 70 after three fabric is noted v1sually. The nature of the e 011 and standard launderings or dry cleanings. The oil repellency the respectlve O11 repenfincy mtmgs are: rating on these fabrics should be a minimum of 5 initially Oil repellency and of 4 after the three launderings or dry cleanings. T l ti ti Representative examples further illustrating the invenn-Heptane 9 tiOH fOliOW! c ll 3 Example 1 -i) 3:323:3 g A sample of cotton wide Wale corduroy was padded "::":'I: 5 to a Wet pickup of 100% With a treatment bath containing 5050 hexade cane 4 g;f% of a mature of copolymers consisting of 40 parts /75 hexadecane/Nujol 3 2 (A) Copolymer of:

Null 0 (1) F(CF CH CH O C(CI-I )C=CH wherein n is 6, 8, and 10 in the ratio of 3 :221 In assigning a rating, for example, 1f a treated fabric rewith small amounts of monomer with ":12 pels the number 1 to 6 solutions but not number 7, its 5 and 14 975 rating 13 a (2) Butyl acrylate 2,0

After obtaining the initial oiland water-repellency (3) NmethYlolacrYlamide 05 ratings of the fabric specimens, portions of them are subjected to three standard launderings and three standard d 60 parts f dry cleanings as a test of the durability of the finish. The 40 laundering test is carried out in a machine described in (B) Copolyrner of:

Federal Specification CCC-T191b, Method 5550. Soft 1) Zethylhexylmethacrylate 98 water is added to the machine to a depth of 5 to 7 inches, (2) N-methylolacrylamide 2 and with fabrics of cotton, polyester fibers, and their blends the water 18 heated to the 3011. F01 other fabrics The 0,46% of the mixed copolymerg was obtained from such as wool, nylon, acetate and their lend th Wa r using 3.5% of a 13% dispersion of the copolymer mixture is heated to C. Neutral Soap in a Con en r i n f stabilized with the acetic acid salt of dimethyloctadecyl- 0.1% based on the weight of water in the machine is amine. The bath also contained 1% of the acetic acid salt added, and, in the case of cotton or polyester fibers, of a condensation product of hexarnethylolmelainine, 0.05% soda ash is also added. Test specimens of fabric 50 stearic acid, and triethanolamine mixed with 0.33 part of together with other fabric specimens to give a total dry parafiin wax per part of condensation product salt load of three pounds are placed in the machine. The (Phobotex f/t/c water repellent supplied by the Ciba fabrics are subjected to Washing action for 40 minutes Company) and 0.1% of the acidic aluminum glycolate when they are removed, rinsed, and squeezed flat. A fabcatalyst. The fabric was dried for 5 min. at 120 C. then ric specimen is dried on a at press at about 150 C. for heated 2 min. at 170 C. (control specimen). Another 30 seconds on each side. It is conditioned at 20 C. and sample of the corduroy was similarly treated with a pad relative humidity for at least 4 hours before makbath the same as above with 0.11% by weight of a ing repellency tests. The dry cleaning test is conducted mixture containing 73% by weight of the sodium salt of in an American Association of Textile Chemists and sulfated G -C alkenyl acetate and 27% by weight of Colorists Standard Launder-Ometer. A specimen, 20 60 the condensation product of 10 moles of ethylene oxide cm. x 25.4 cm., is placed in a 500 ml. jar with 150 ml. and 1 mole of technical oleyl alcohol (exhibit specimen). of tetrachloroethylene, 2.25 -g. of acommercial dry clean- The initial water repellency (spray rating) and oil ing detergent, and 0.15 g. of water. The jar is placed in repellency and the durability of these repellencies after the Launder-Ometer and tumbled for 20 minutes at 27 three standard launderings and dry cleanings as described C. Excess solvent is removed by blotting between blotabove are as follows:

Water Repelleney Oil Repellency Fabric After 3 After 3 After 3 After 3 Initial Laun- Dry Initial Laun- Dry derings Cleanings derings Cleauings Control 100 so 5 4 0 Exhibit 100 so 7 7 6 The significant improvement in the finish of this fabric provided by the surfactant adjuvants is the increased initial oil repellency, its retention during repeated launderings n C) durability of these repellencies after three standard dry cleanings are as follows:

and dry cleaning, and the retention of the water repel- Water Repelleney Oil Repelleucy lency during laundering. Fabric L Example 2 Initial girlligsy Initial Atleaggiggrsy A sample of wool flannel was padded to a wet pickup of 75% with a treatment bath containing 0.65% by weight z t q 3 8 2 of the fiuoroalkyl-containing copolymer mixture of Exam- 1 0 pel l and 0.8% of Phobotex f/t/c" water repellent with 0.08% catalyst. The fabric was air-dried then heated 7.5 A d fi it increase i h i i i l Water repenency, a u s a C. (COIltTOl p n- Another Sample marked improvement in the oil repellency, and a high of the W001 fiamlfil Was Similarly Padded with a bath the retention compared to a complete loss of these properties same as above except that 0.169% by weight of a mixture 15 during repeated d cleanings are to b t d containing 75 by weight of the sodium salt of sulfated wh h f oi treatment was given t specimens ir a: allienyl acetate and 33% by Weight of the C011 of a 55/45 polyester fiber/cotton fabric the following densation product of 10 moles of ethylene oxide and 1 results were b i d; mole of p-nonylphenol was added (exhibit specimen). The initial water repellency nd oil repellency and the Water Repellency Oil Repellcncy durability of these repellencies after three standard dry cleanings are as follows: Fabnc Initial After 3 Dry Initial After 3 Dry Clcanings Cleanings Water Repelleney Oil Repellency 4 0 4 Control 90 K0 Tabw Initial Atte1-3Dry Initial AftcrEDry a Exmb 100 7 4 Cleauings Clcanings A particularly significant improvement is the higher inigoto iii?) (1) so tial oil repellency and a retention of this property during dry cleaning. 1 N data. Example 4 A high oil repellency is imparted to the fabric which aceiate Velvat i g was paddei ath27 a g without the invention treatment is devoid of this property, i of 100% Wu a treatment at con ammg y and the finish survives repeated dry cleanings. welght P ercent When the foregoing treatment was repeated with wool 1' I t f gabardine with the employment of the condensation prod- Fluoloahyl'comdnmg Copo ymer m M ure 0 0 33 net of 10 moles of ethylene oxide and 1 mole of technical P16 1 "I, "f 8 oleyl alcohol in place of the ethylene oxide/p-nonylphenol Phobotex f/t/c Water lepe lent d condensation produce for the exhibit sample the same 40 u 1 Tartaric acid 0- su ts were obtained. d With wool flannel the treatment as first given in the Emylene oxlde/pnonylpncnol condensalon pro example was repeated replacing 0.8% of the Phobotex of Example 2 f/t/c water-repellent with 6% of a 28% by weight disper- The fabric was dried at 135 C. and heated ten minutes sion of the wax/copolymer composition of Example 4 of at 160 C. (control fabric). A second portion of the fab- British Patent 915,759 wherein the copolymer was preric was treated in the same way with 0.076% by weight of pared from 30 Parts y Weight of y yl a mixture of the anionic and nonionic surfactants of Exrnethacrylate and 70 parts by weight of octadecyl methample 3 added to the padding bath (exhibit fabric). The acrylate and the ratio of wax to copolyrner was 3 to 1. re ellency tests of these treated fabric specimens are as The initial water and oil repellencies are as follows: follo Fabric Water Repellency Oil Repellency Water Repellency Oil Repellency Fabric Control 80 2 Initial After 3 Dry Initial After 3 Dry Exhibit 9O 5 Cleanings cleanings A significant improvement in the repellency of both water $8 Z8 3 i and oil is obtained.

Example 3 A significant improvement in both the water and oil re- A 55/45 polyester fiber/wool suiting fabric was padded p y is achieved, and these Properties dry clean at 27 C. to a wet pickup of with a treatment bath gcontaining 0.52% by weight of the fluoroalkyl-containing Example 5 copolymer mixture of Example 1 and 1.0% of Phobotex f/t/c water repellent with the usual 0.1% of catalyst for 5 A wool suiting fabric was padded at 32 C. to a Wet this water repellent. The fabric was dried at about C. pickup of 65% with a treatment bath containing 0.75% and heated for five minutes at C. (control specimen). by weight of the iiuoroalkyl-containing copolymer mix- Another sample of the fabric was given the same treatture of Example 1 and 0.92% of Phobotex f/t/c water ment except L131; now the pad bath contained in addition repellent with 0.09% catalyst. The fabric was dried and to the oil and water repellency agents, 0.127% by weight 70 cured 7.5 minutes at C. (control). A second portion of a mixture containing 74% by weight of the sodium salt of sulfated C C alkenyl acetate and 26% by weight of the condensation product of ethylene oxide and technical oleyl alcohol used in Example 1 (exhibit specimen). The initial Water repellency and oil repellency and the of the fabric was treated in the same Way except the bath contained an added component amounting to 0.17% by weight of the bath of a mixture of 75% sodium dodecyl sulfate and 25% of the ethylene oxide/technical oleyl alcohol condensation product of Example 1 (exhibitspetk' 10 The fabric was padded to a 100% pickup, dried at 135 C., and heated 1.5 minutes at 163 C. followed by a mild alkaline wash and ironing at 150 C. (exhibit specimen).

Water Repellency on Repellellcy A control specimen was prepared by the same procedure Fabric except the sodium sulfated alkenyl acetate was omitted Initial After 3 Dry Initial Aft r 3 Dry from the pad bath. The fabric specimens were tested for cleanings cleanings initial water and oil repellency and for retention of the oil repellency during three dry cleanings with the results Eiiiiiiiiijjjii: 133 8 i 3 An enchantment of the initial water and oil repellency and gis O11 Repellency improvement in retention of the oil repellency during re- Fabric After peated dry cleaning by the addition to the treatment bath igg Initial g gs; of the mixture of surfactants are apparent. 15 cleanings Example 6 ControL 0 6 2 A wool suiting fabric was padded at 32 C. to a Wet Exhibit 80 7 6 pickup of 75% with a treatment bath containing 0.84% by weight of a copolymer of 50/50 2(N-propylhepta- The marked effect of the addition of the anionic agent to decafluorooctylsulfonamido)ethyl acrylate/chloroprene. the pad bath on the durability to repeated dry cleaning of This fiuoroalkyl-containing copolymer mixture was added the water and oil repellency is apparent. to the bath as a 28% water dispersion as described in Example 8 U.S.P. 2,803,615. The treatment bath also contained 0.8% by weight of Phobotex f/t/c water repellent with 0.08% A textfle fimshmg pad bath was Prepared to contam' catalyst. The fabric was then dried and cured 7.5 min- Percent utes at 150 C. (control). A second portion of the fabric Fluoroalkyl contammg copolymer mlxmre of was treated in the same way but with 0.14% by weight 1 of a mixture of 75% sodium dodecyl sulfate and 25% of Phobotax f/t/c water repellent the ethylene oxide/technical oleyl alcohol condensation Catalyst 012 product of Example 1 added to the treatment bath (Ex- 30 if tnfizme crease reslstant resm Aerotex hibit A). A third portion of the same fabric was treated 23 Amencan Qyanamld) like Exhibit A with sodium hexadecyl sulfate employed as i m chlonde the anionic component of the added surfactant mixture Tartan: acld (1025 (Exhibit B). The following repellency test results were ob- ISORTOPYI alcohQl m Sodium salt of sulfated C -C alkeny-l acetate 0.033 Cotton rainwear fabric was padded at 30 C. to 100% Water Repelleney Oil Repelleney pickup in the above bath, dried at 135 C., and heated 2.5 Fabric minutes at 170 C. The cured fabric was then washed in Initial After 3 Dry Initial Aiter3 Dry a bath at C. containing 0.1% soda ash and 0.05% Cleamngs Cleanmgs sodium dodecyl sulfate, followed by rinsing at 50 C. and

ironing at 150 C. (exhibit specimen). A control specigggggi'g fjjjjjjjj 38 Z8 5 2 men was prepared by the same procedure except the sodi- EXhibitB 100 80 6 4 um sulfated alkenyl acetate was omitted from the pad bath. The fabrics were tested with the results shown be- In each case the addition to the treatment bath of the 0 low:

Water Repellency Oil Repelleney Fabric After 3 After 3 After 3 After 3 Initial Laun- Dry Initial Laun- Dry derings Cleanings derings Cleanings Control 100 70 70 7 4 5 7 Exhibit 100 90 90 7 7 7 mixture of the anionic and the non-ionic surface active Significant effects of the added surface active agent are agents has effected an improvement in the initial water and the increased retention of water repellency during repeated oil repellency. The retention of these properties during laundering and repeated dry cleaning and of oil repellency repeated dry cleanings relative to the control is little during repeated laundering. changed.

Examp 1e 7 Example 9 An aqueous treatment bath for padding a fabric COB-S1815 on n 1 guii gg gg f :ggifig fiber/cotton c ta! e A textile finishing pad bath consisting of:

Percent 5 Percent Fluoroalkyl-containing polymer mixture of Exam- Fluoroalkyl-containing copolymer mixture of ample 1 0.52 EX. 1 0.32 Phobotex f/t/c water repellent 1.0 Phobotex f/t/c Water repellent 1.0 Catalyst 0.1 Catalyst 0.1 Modified triazine crease resistant resin (Aerotex Urea-formaldehyde crease resistant resin 4.0 2 --American Cyanamid) 3.6 Magnesium chloride 0.25 Melamine formaldehyde crease resistant resin Tartaric acid 0.06 (Resin M-3) 1.7 Isopropyl alcohol 2.0 Zinc nitrate 0.64 Sodium salt of sulfated G -C alkenyl acetate 0.007

Sodium salt of sulfated C 43 alkenyl acetate 0.017

Water to make 100.00

Cotton print fabric was padded at 33 C. to 100% pickup in the above bath, dried at 135 C., and heated three minutes at 170 C. Another portion of the fabric was similarly padded without the sodium sulfated alkenyl acetate in the pad bath and dried and cured in the same way to provide a control specimen. The results of repellency tests on the two fabric specimens are as follows:

sists of adding to the dilute treatment bath, with agitation, at to 15% aqueous solution of a mixture consisting of (A) 60 to 75 parts by weight of a member of the group consisting of (I) sodium C to C alkyl sulfates and (II) the sodium salt of a sulfated C to C alkenyl acetate and (B) 40 to 25 parts by weight of a condensation product of 10 to 20 moles of ethylene oxide and 1 mole of a In the above treatment the added anionic agent has definitely increased the durability of the water repellency to repeated laundering and dry cleaning and markedly improved oil-repellency finish for resisting repeated dry cleaning.

' The preceding representative examples may be varied within the scope of the present total specification'disclosure, as understood and practiced by one skilled in the art, to achieve essentially the same results.

As many apparently widely different embodiments of this invention may be. made without departing from the spirit and scope thereof, itis to be understood that this invention is not limited to the specific embodiments thereof except as defined in the appended claims.

The embodiments oi the inventionin which an exclusive property or privilege is claimed are as follows.

Weclaim:

1. In the process of treating textile fabric with a dilute treatment bath comprising (a) a fluoroalkyl-containing polymeric composition to impart oiland water-repellency, and (b) a composition comprising 1) a wax and a member of the group consisting of(2) the acetic acid salt of a condensation product of hexamethylolmelamine, stearic acid, and triethanolamine and (3) a copolymer of '2-(diethylamino)ethyl methacrylate and octadecyl methacrylate as a water repellent, the improvement which conmember of the group consisting of C to C alkenyl alcohol and p-nonylphenol to provide from about 15% to about 30% by. weight of said mixture on the basis of said fiuoroalkyl-containing polymeric composition and impregnating the fabric with the resultant treatment bath.

2. A process according to claim 1 wherein the treatment bath contains said component (a) in an amount to give a pickup on the weight of the fabric from about 0.2% to about 0.5% of the component, and said component (b) is present to the extent of 1 part to 5 parts per part of said component (a).

WILLIAM D. MARTIN, Primary Examiner.

T. G. DAVIS, Assistant Examiner. 

1. IN THE PROCESS OF TREATING TEXTILE FABRIC WITH A DILUTE TREATMENT BATH COMPRISING (A) A FLUOROALKYL-CONTAINING POLYMERIC COMPOSITION TO IMPART OIL- AND WATER-REPELLENCY, AND (B) A COMPOSITION COMPRISING (1) A WAX AND A MEMBER OF THE GROUP CONSISTING OF (2) THE ACETIC ACID SALT OF A CONDENSATION PRODUCT OF HEXAMETHYLOLMELAMINE, STEARIC ACID, AND TRIETHANOLAMINE AND (3) A COPOLYMER OF 2-(DIETHYLAMINO) ETHYL METHACRYLATE AND OCTADECYL METHACRYLATE AS A WATER REPELLENT, THE IMPROVEMENT WHICH CONSISTS OF ADDING TO THE DILUTE TREATMENT BATH, WITH AGIATION, A 5% TO 15% AQUEOUS SOLUTION OF A MIXTURE CONSISTING OF (A) 60 TO 75 PARTS BY WEIGHT OF A MEMBER OF THE GROUP CONSISTING OF (I) SODIUM C12 TO C16 ALKYL SULFATES AND (II) THE SODIUM SALT OF A SULFATED C16 TO C18 ALKENYL ACETATE AND (B) 40 TO 25 PARTS BY WEIGHT OF A CONDENSATION PRODUCT OF 10 TO 20 MOLES OF ETHYLENE OXIDE AND 1 MOLE OF A MEMBER OF THE GROUP CONSISTING OF C16 TO C18 ALKENYL ALCOHOL AND P-NONYLPHENIOL TO PROVIDE FROM ABOUT 15% TO ABOUT 30% BY WEIGHT OF SAID MIXTURE ON THE BASIS OF SAID FLUOROALKYL-CONTAINING POLYMERIC COMPOSITION AND IMPREGNATING THE FABRIC WITH THE RESULTANT TREATMENT BATH. 